Emulsion Polymerization Technique Research Articles

Achieving optimum balance between mechanical properties and gloss of acrylonitrile–styrene–acrylate resin through control of rubber particle size distribution

AbstractPreparation of acrylonitrile–styrene–acrylate (ASA) with high gloss and superior impact properties is still challenging. Here, we developed a new strategy for the preparation of ASA resins by a selective redox initiation method based on a semi‐continuous emulsion polymerization technique. A series of ASA core‐shell impact modifiers were firstly obtained by grafting styrene (St) and acrylonitrile (AN) onto poly(n‐butyl acrylate) (PBA) seeded latexes of different sizes. The ASA core‐shell impact modifier was then used to toughen the styrene–acrylonitrile copolymer (SAN). The synergistic effects between the single particle size of the rubber phase and different particle sizes were systematically investigated, and the mechanical properties of SAN‐toughened resins at various particle sizes of the rubber phase were analyzed. The results revealed that toughened SAN with small particle sizes possessed better gloss, and the impact strength of the doped small‐particle toughened SAN was much higher than that of the single particle size toughened SAN. The ASA graft powders synthesized from large particle PBA (particle size 316 nm) and small particle PBA (particle size 99 nm), respectively, were mixed at a 50/50 ratio and blended with SAN resin, a gloss level reaching 95, and an impact performance of 275 J/m values almost twice those of a single particle size toughened SAN.Highlights Acrylonitrile–styrene–acrylate resins with an impact strength of 275 J/m and gloss of 95 were prepared. The balance between mechanical properties and gloss of acrylonitrile–styrene–acrylate resin was obtained. Polymerization was initiated at low temperature.

Enhancement of interaction between Shenhua coal and GON-based dispersant with “surface-to-surface” adsorption by regulating the oxidation degree of GON: Experiments and simulations

The present study focuses on the synthesis of several graphene oxide nanosheet (GON)-based dispersants with an adsorption mode of “surface-to-surface” for the preparation of Shenhua coal (SC) water slurry (SCWS), achieved by grafting allyl polyoxyethylene ether (APEG) onto GON edges with varying degrees of oxidation using emulsion polymerization and esterification techniques. The impacts of the oxidation degree of GON on its structural characteristics and the performance of GON-based dispersants in SCWS were comprehensively assessed through a range of experimental techniques, alongside molecular dynamics (MD) simulations. Results demonstrated that with the increase in oxidation degree, there was an elevation of oxygen-containing groups, in which the content of COH decreased while the content of COC increased. Among all dispersants, GA-2, which was synthesized using GON-2 as the raw material with a graphite-to-KMnO4 mass ratio of 1:2.5, exhibited superior viscosity-reducing and stabilizing abilities compared to other dispersants. All SCWSs demonstrated pseudoplastic fluid behavior and showed good agreement with the Herschel-Bulkley model. After the adsorption of dispersants in SC, both the Zeta potential and surface wettability of SC significantly improved, especially with GA-2. The interaction mechanism between the dispersant and SC was analyzed by establishing and employing three adsorption models (M-1, M-2, and M-3). The interfacial adsorption structure confirmed that the dispersant exhibited “surface-to-surface” mode on coal through hydrophobic interaction, hydrogen bonding, and π–π interaction. Energy studies revealed that M-2 with the highest Eads (−105.31 kcal/mol) demonstrated superior adsorption strength compared to M-1 and M-3. Investigations into water molecule mobility revealed that the interaction between the GON-based dispersant and SC resulted in a reduction of water molecule mobility, thereby promoting water molecule aggregation to facilitate the formation of hydration films and enhance SCWS stability. In summary, an optimal oxidation degree of GON was found to be crucial for enhancing the performance of GON-based dispersants; higher oxidation levels may hinder dispersant adsorption on coal surfaces by converting hydroxyl and carboxyl groups into epoxide groups, thus impairing the conjugated structure.

Dual Temperature and pH Sensitive Poly(ethyl methacrylate‐co‐acrylamide) Nanogels Have Potential for Controlled Release of Doxorubicin

AbstractIn this study, the synthesis and characterization of poly(ethyl methacrylate‐co‐acrylamide) (i.e., poly(EMA‐co‐AAm)) nanogels and the loading and release studies of doxorubicin hydrochloride were carried out. The synthesis of nanogels was carried out using the emulsion polymerization technique at 60 °C. Swelling experiments showed that the nanogels were sensitive to temperature and pH of the medium. Zeta sizer analysis results showed that the synthesized nanogels had an average size of 23.17 nm and the PDI value was 0.270. In the loading studies of doxorubicin into nanogels, the drug loading capacity (DLC) of the nanogel was determined as 32% and the drug loading efficiency (DLE) was determined as 77%. Release studies conducted at pH = 5.4 and pH = 7.4 at 37 °C showed that the release percentage was 17% even in 32 h at pH = 7.4, and 82% in 5 h at pH = 5.4. Release studies conducted at different temperatures at pH = 5.4 revealed that the release percentage was 82% at 37 °C, 85% at 39 °C, and 89% at 41 °C. These results revealed that poly(EMA‐co‐AAm) nanogels can be used in targeted controlled release of doxorubicin and can increase drug effects while reducing side effects.

Formulation and Evaluation of Lungs-Specific Doxorubicin-Loaded Chitosan-PLGA-Alginate Polymeric Nanoparticles

Background: An antibiotic called doxorubicin is produced by the Streptomyces peuce-tius bacterium, which is a member of the anthracycline drug class and is used in chemotherapy. Usually, doxorubicin is employed to cure solid tumors in children and adult patients. The physical and biological stability of the medicine can be increased by encasing it in nanoparticles, which increases the active pharmaceutical ingredient's bioavailability. Objective: This study aimed to create lungs targeting doxorubicin-loaded biodegradable polymer-ic nanoparticulate system by utilizing an appropriate method and conducting its evaluation. Methods: The polymeric nanoparticles using biodegradable polymers were prepared by the emul-sion polymerization method. Franz- diffusion cells were utilized to conduct in-vitro drug diffu-sion investigations. Results: Based on the outcomes of the experiments carried out for the research, polymeric nano-particles of doxorubicin were prepared utilizing different concentrations of chitosan, Sodium al-ginate, and PLGA. The visual appearance of doxorubicin polymeric nanoparticles shows homo-geneous dispersion with no phase separation form. The percentage yield, % entrapment efficien-cy, and drug content obtained for the final formulation were 93.43 ± 1.776, 87.31 ± 1.075, and 91.98 ± 0.493, respectively. A size dimension of 174.51 nm with a PDI of 0.242 and zeta poten-tial value of -36.1 mV of prepared nanoparticles demonstrate the stability of the formulation. The presentation of the PNPs of the optimized formulation having 310mg Tween 80 showed in vitro diffusion of 98.93% ± 0.296 % and an increased flux rate. Based on the determination coeffi-cients, the Higuchi model (K0 = 20.43 and R2= 0.982) was determined to have the best fit for the release data. Conclusion: Based on the trials conducted during the investigation, it was determined that the emulsion polymerization technique was best for the fabrication of the polymeric nanoparticles by utilizing different concentrations of chitosan, Sodium alginate, and PLGA. The formulation F6 containing 310mg Tween 80 suggested improved in vitro diffusion following the Higuchi model throughout all formulations. The findings suggest that a sustained process was responsible for the drug's release from the doxorubicin polymeric nanoparticles.

Mini review polyurethane hybrids: preparation, characterization and applications

Polyurethane hybrids (PUHs) are a type of versatile materials with a broad variety of possible applications. Considering the connections between their structure and characteristics, this is especially true. Because of its special mechanical stability, toughness, stickiness, sustainability of the finished product, biological properties, and chemical properties, PUHs are the subject of extensive research and development for use in a wide range of applications. Polyurethane /acrylic hybrids are important type of binders in coating industries due to their exceptional properties. This mini review aims to provide an overview of different types of polyurethane/acrylic hybrids, including waterborne, blending, and UV curable hybrids. The synthesis of these hybrids through addition and emulsion polymerization techniques is discussed, emphasizing the importance of achieving intimately homogenous latex. The hybrids (PUHs) enhanced the physical, chemical, and mechanical properties of the final products including coatings, paints, adhesives, and performance of other products. In addition, the anticorrosion coatings based on PUHs exhibits the properties of polyurethane and acrylic to reduce or prevent the corrosion.

The Paradoxical Behavior of Rough Colloids at Fluid Interfaces.

Colloidal particles adsorb and remain trapped at immiscible fluid interfaces due to strong interfacial adsorption energy with a contact angle defined by the chemistry of the particle and fluid phases. An undulated contact line may appear due to either particle surface roughness or shape anisotropy, which results in a quadrupolar interfacial deformation and strong long-range capillary interaction between neighboring particles. While each effect has been observed separately, here we report the paradoxical impact of surface roughness on spherical and anisotropic ellipsoidal polymer colloids. Using a seeded emulsion polymerization technique, we synthesize spherical and ellipsoidal particles with controlled roughness magnitudes and topography (convex/concave). Via in situ measurement of the interfacial deformation around colloids at an air-water interface, we find that while surface roughness strengthens the quadrupolar deformation in spheres as expected by theory, in stark contrast, it weakens the same in ellipsoids. As roughness increases, particles of both shapes become more hydrophilic, and their apparent contact angle decreases. Using numerical predictions, we show that this partially explains the decreased interfacial deformation and capillary interactions between the ellipsoids. Therefore, particle surface engineering has the potential to decrease the capillary deformation by asymmetric particles via changing their capillary pinning, as well as wetting behavior at fluid interfaces.

Long-chain alkyl groups enhance the water-repellent properties of short-chain perfluoroalkyl compounds: An experimental and computer simulation study

The polymers composed of long-chain stearyl acrylate (SA) and short-chain (perfluorohexyl) ethyl methacrylate (FA) were synthesized using the emulsion polymerization technique. Cotton fabric was then coated with these polymers to act as a water-repellent agent. Surface wetting properties of the coated cotton fabric were tested. In a peculiar manner, the water repellency of the coatings did not improve with the increase of the perfluorohexyl group. Therefore, the polymer's crystallization behaviors and melting temperature were assessed through differential scanning calorimetry (DSC) and computer simulation. A computer simulation was employed to analyze the density, surface energy, element distribution, chain arrangement, bond order parameter, and surface images of the polymer film. The results suggest that water repellency is not directly related to the film's surface energy but rather depends on the element proportion, bond angle distribution, and dihedral angle torsion energy. The key points will serve as invaluable indicators for the development of a highly efficient water-repellent coating with a low proportion of fluorine and provide a more sustainable solution for water-repellent applications.

Extending Polymer Opal Structural Color Properties into the Near-Infrared

We report the fabrication and characterisation of near-IR reflecting films and coatings based on shear-assembled crystalline ensembles of polymer composite microspheres, also known as “polymer opals”. Extension of the emulsion polymerisation techniques for synthesis of tractable larger core-interlayer-shell (CIS) particles, of up to half a micron diameter, facilitates the engineering and processing of thin-film synthetic opals, with a tunable photonic stopband spanning an extended spectral range of λ ≈ 700–1600 nm. Samples exhibit strong “scattering cone” interactions, with considerable angular dependence and angle tuning possible, as measured with a goniometric technique. These intense optical resonances in the near-IR, particularly within the important region around λ ~ 800 nm, combined with an appreciable translucency within the visible light spectrum, is indicative of the potential applications in coatings technologies and solar cells.

Fabrication of cationic microgels doped MnO2/Fe3O4 nanocomposites, and study of their photocatalytic performance and reusability in organic transformations

AbstractThis article reports, the fabrication of cationic microgel doped MnO2/Fe3O4 nanocomposites (CM@MnO2/Fe3O4) via free radical emulsion polymerization technique, and an economical and environmental friendly approach to some organic transformations, such as heterogeneous photocatalytic reduction of methylene blue (MB, toxic dye), para‐nitro phenol (PNP, harmful pollutant) and dimethyl amino benzaldehyde (DMAB, skin allergic reagent) in presence of UV light (38 W). First of all, three different crosslinked grades of cationic microgels (CMs) have been synthesized by using styrene, dimethyl acrylamide, cyclohexyl methacrylate, [2‐(acryloyloxy)ethyl] trimethylammonium chloride and N‐hydroxymethyl acrylamide monomers by taking different amounts of N‐hydroxymethyl acrylamide, and keeping the other monomers in fixed quantities. Further, all the grades of CMs have been doped by bimetallic MnO2/Fe3O4 nanoparticles, through hydrothermal method. Fabrication of CMs and CM@MnO2/Fe3O4 nanocomposites has been confirmed by the characteristic peaks observed in FT‐IR spectral analysis and their thermal stability has been evidenced by thermogravimetric analysis. TEM and DLS analyses have revealed their particular size. The surface morphology of CMs and CM@MnO2/Fe3O4 nanocomposites has been visualized by scanning electrode microscope analysis. The nanocomposites have effectively and efficiently catalyzed the reduction reactions of MB, PNP, and DMAB, in presence of UV light, by 98%, 98%, and 86%, respectively. The photocatalysts have been reused up to eight cycles without any loss of their catalytic activity. The photocatalytic reductions have also been studied for their kinetics, and exhibited pseudo first order kinetics (kapp, 10−2 min−1).

Iron oxide nanoparticle-stabilized Pickering emulsion-templated porous scaffolds loaded with polyunsaturated fatty acids (PUFAs) for bone tissue engineering.

Dietary intake of ω-3-polyunsaturated fatty acids (PUFAs) can significantly improve the expression levels of alkaline phosphatase (ALP) and osteocalcin. However, PUFAs are hydrophobic and highly sensitive to temperature, oxygen concentration, pH, and ionic strength. Hence, it is challenging to use PUFAs as bioactive compounds for bone tissue engineering. Here, we encapsulated PUFAs in liposomes to improve their stability. The hydrodynamic size of the PUFA-loaded liposomes was found to be 121.3 ± 35 nm. GC-MS analysis showed that the encapsulation efficiency of the PUFAs was 19.9 ± 3.4%. These PUFA-loaded liposomes were loaded into porous scaffolds that were prepared by polymerizing glycidyl methacrylate and trimethylolpropane triacrylate monomers using the Pickering emulsion polymerization technique. Oleic acid-coated iron oxide nanoparticles were used as the stabilizing agent to prepare these acrylate-based scaffolds containing PUFA-loaded liposomes (P-Lipo-IO(GMA-TMPTA)). SEM micrographs confirmed the porous nature of the scaffolds and the presence of well-adhered liposomes. An in vitro cytotoxicity study conducted using MG63 cells confirmed that these scaffolds showed desirable cytocompatibility. Cell adhesion study showed a well-spread morphology, indicating firm adhesion of the cells. The alizarin red staining of P-Lipo-IO(GMA-TMPTA) scaffolds showed 3- and 2-fold higher calcium deposition compared to the control on days 7 and 14, respectively. ALP activity was also 2-fold higher than that of the control on day 14. RT-PCR analysis of cells exposed to P-Lipo-IO(GMA-TMPTA) scaffolds showed significantly higher expression of osteogenic markers compared to the control. An antibacterial study conducted on Staphylococcus aureus showed a higher percentage inhibition and reactive oxygen species generation in samples treated with P-Lipo-IO(GMA-TMPTA) scaffolds. These desirable biological properties indicate that the developed scaffolds are suitable for bone tissue engineering.

Synthesis and characterization of novel poly cysteine methacrylate nanoparticles and their morphology and size studies.

Polymer nanoparticles (PNPs) have significantly advanced the field of biomedicine, showcasing the remarkable potential for precise drug delivery, administration of nutraceuticals, diagnostics/imaging applications, and the fabrication of biocompatible materials, among other uses. Despite these promising developments, the invention faces notable challenges related to biodegradability, bioactivity, target-site specificity, particle size, carrier efficiency, and controlled release. Addressing these concerns is essential for optimizing the functionality and impact of PNPs in biomedical applications. Here, new poly cysteine methacrylate nanoparticles (PCMANPs), ca. (200 nm) in size have been synthesized from the cysteine methacrylate (CysMA) monomer using different strategies, including emulsion and inverse emulsion polymerization techniques. The monomer was synthesized using the Michael addition reaction, involving the addition of 3-(acryloyloxy)-2-hydroxypropyl methacrylate to the sulfhydryl group (-SH) of the cysteine (Cys) active site, with the aid of dimethyl phenyl phosphine (DMPP) as a nucleophilic agent as previously reported. To enhance nano-polymerization, a thorough exploration of various initiators, including ammonium persulfate (APS) and 4,4'-azobis (4-cyanovaleric acid) (ACVA), alongside surfactants, such as polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), and sodium dodecyl sulfate (SDS), was conducted. Additionally, critical parameters, such as reaction time, temperature, and solvents, were systematically investigated due to their substantial influence on the shape, size, stability, and morphology of the synthesized polymer nanoparticles. This comprehensive approach aims to optimize the synthesis process, ensuring precise control over the key characteristics of the resulting nanoparticles for enhanced performance in diverse applications. Various characterization techniques, including field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), nuclear magnetic resonance (NMR), Raman spectroscopy, Fourier-transform infrared spectroscopy (FTIR), zeta potential, and zeta sizer dynamic light scattering (DLS) analysis, were utilized to investigate purity, morphology, and particle size of the PNPs. As a result, a spherical, monodispersed (homogenized), and stable PCMANP with defined size and morphology was achieved. This may exhibit a remarkable achievement in the future of drug delivery systems and therapeutic index.

Synthesis of silane- and quaternary ammonium-bearing copolymers and application as a coating resin on cotton fabric.

In this study, silane and quaternary ammonium functional methacrylate monomers were synthesized and used to construct a copolymer using an emulsion polymerization technique to control the reaction rate. The copolymer was then designed using different ratios of silane and quaternary ammonium groups to investigate the relationship between the structure and properties. The presence of the ethoxy silane group in the copolymer series provided covalent bonding through the silanol group onto cotton fabric. The presence of cationic groups also helped to cover the fabric surface. After coating the cotton textile fabric, the resistance of the dye on the fabric surface to friction was assessed and tests were conducted on washing, rubbing, water, and light fastness. Finally, the textile surfaces were investigated for their antibacterial activity against Staphylococcus aureus and Escherichia coli. It was observed that the copolymer series showed >99% killing efficiency against S. aureus but had no effect on E. coli.

PH-Sensitive Acrylic Terpolymers for the Coating of Orally Administered Drugs Used for Colonic Release.

Polymeric coatings are a promising option for the development of delivery systems for orally administered drugs. However, the gastrointestinal conditions to which they are subjected, which include low pH and solubility as well as peristaltic movements, can limit their applications. In this work, different formulations of polymeric coatings were produced using pH-sensitive materials consisting of copolymers of methyl acrylate, methyl methacrylate, and methacrylic acid. The polymers were synthesized by the emulsion polymerization technique, obtaining small average particle sizes (56-190 nm), molecular weights between 200,000 and 400,000 g/mol, and a glass transition temperature above 35 °C, which are suitable for film formation at room temperature. Thus, they were assessed as coatings for hydroxypropyl methylcellulose capsules (HPMC) using the immersion method, showing adequate capacity to protect the capsule at gastric pH (pH 1.2) and dissolve at the simulated intestinal pH (pH= 7.2). In particular, the higher the content of the acidic monomer, the higher the release time of the test molecule contained in the acrylic terpolymer-coated HPMC capsules proposed, which was a curcuminoid derivative due to their bright color and potential medical benefits. In addition, a minimum number of immersions was required for coating the HPMC capsules at high acidic concentrations, which further facilitates the delayed release needed for colonic treatment. However, too high proportions of methacrylic acid may result in cytotoxicity issues. Consequently, a biocompatible formulation containing a proportion of methyl acrylate, methyl methacrylate, and methacrylic acid of 7:3:3 is proposed as the most adequate for colonic release. Thus, by chemically modulating the molar percentages of the acrylic monomers, it was possible to obtain tailored acrylic terpolymer coatings with different characteristics and desired properties in order to modulate the release kinetics of an active substance in a colonic environment.

MXene Clay (Ti2C)-Containing In Situ Polymerized Hollow Core-Shell Binder for Silicon-Based Anodes in Lithium-Ion Batteries.

Silicon, an attractive anode material, suffers fast capacity fading due to the electrical isolation from massive volumetric expansion upon cycling. However, it holds a high theoretical capacity and low operation voltage in its practical application. In this study, a new water-based binder, MXene clay/hollow core-shell acrylate composite, was synthesized through an in situ emulsion polymerization technique to alleviate the fast capacity fading of the silicon anode efficiently. The efficient introduction of conductive MXene clay and the hollow core-shell structure, favorable to electron and ion transport in silicon-based electrodes, gives a novel conceptual design of the binder material. Such a strategy could alleviate electrical isolation after cycling and promises better electrochemical performance of the high-capacity anodes. The effect of the MXene introduction and hollow core-shell on the binder performance is thoroughly investigated using various characterization tools by comparison with no MXene-containing, core-shell acrylate, and commercial styrene-butadiene latex binders. Consequently, the silicon-based electrode containing the MXene clay/hollow core-shell acrylate binder exhibits a high capacity retention of 1351 mAh g-1 at 0.5C after 100 cycles and good rate capability of over 1100 mAh g-1 at 5C.

Europium recovery process by means of polymeric nanoparticles functionalized with acrylic acid, curcumin and fumaramide

Polymeric nanoparticles of poly(methyl methacrylate) were obtained by emulsion polymerization techniques in a process of two stages. The particles were functionalized with acrylic acid, curcumin, and fumaramide and three series of polymeric particles were obtained. The incorporation of functional groups was confirmed by Fourier transform-infrared spectrosocopy (FT-IR) and ultraviolet–visible (UV–Vis) methods. The spherical morphology of particles with an average diameter of 100 nm was observed by scanning electron microscopy (SEM). The polymeric materials were used for recovery of [Eu] from synthetic solutions. The nanoparticles show excellent chelation capacity to trap rare-earth ions, because they recover more than 85% of [Eu] at pH of 2. The images of SEM after extraction process show arrays between particles with larger average particle sizes to 1.5 μm. In addition, the particles have a good stripping capacity, exceeding 50% of it, maintaining their homogeneity in morphology and good stability in dispersion for the recovery and stripping processes. A pseudo-second model order is obtained for the extraction and stripping processes while the best results of stripping process are obtained at pH of 6.

Antibacterial and angiogenic potential of iron oxide nanoparticles-stabilized acrylate-based scaffolds for bone tissue engineering applications

Pickering emulsion polymerization, stabilized by inorganic nanoparticles such as iron oxide nanoparticles (IONPs), can be used to fabricate scaffolds with the desired porosity and pore size. These nanoparticles create stable emulsions that can be processed under harsh polymerization conditions. IONPs, apart from serving as an emulsifier, impart beneficial bioactivities such as antibacterial and pro-angiogenic activity. Here, we coated IONPs with three different weights of oleic acid (5.0 g, 7.5 g, and 10.0 g) to synthesize oleic acid-IONPs (OA-IONPs) that possess the desired hydrophobicity (contact angle > 100°). Next, glycidyl methacrylate and trimethylolpropane triacrylate were polymerized using the Pickering emulsion polymerization technique stabilized by the OA-IONPs. The physicochemical properties of the resulting porous scaffolds were thoroughly characterized using scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), vibrating sample magnetometry (VSM), and a universal testing machine (UTM). The SEM images confirmed the formation of a porous scaffold. The IONPs content, measured using inductively coupled plasma mass spectrometry (ICP-MS), was in the range of 22–26 µg/mg of the scaffold. The mechanical strengths of the scaffolds were in the range of cancellous bone. The degradation profile of the scaffolds varied between 29% and 41% degradation over 30 days. In vitro cytotoxicity studies conducted using the fibroblast (L929) and osteosarcoma (MG-63) cell lines proved that these scaffolds were non-toxic. SEM images showed that the MG-63 cells adhered firmly to the scaffolds and exhibited a well-spread morphology. The antibacterial activity was confirmed by percentage inhibition studies, SEM analysis of bacterial membrane distortion, and reactive oxygen species (ROS) generation in the bacteria. Chick chorioallantoic membrane assay showed that the total vessel length and branch points were significantly increased in the presence of the scaffolds. These results confirm the pro-angiogenic potential of the fabricated scaffolds. The physicochemical, mechanical, and biological properties of the material suggest that the developed scaffolds would be suitable for bone tissue engineering applications.

Acrylic Finished Leather Upgraded with Thermoplastic Polyurethane Filament using 3D Printing – A New Generation Hybrid Leather of Synthetic and Natural Polymer

Leather manufacturing process involves a lot of waste disposal which pollutes environment, some of the processes are inevitable. In the present investigation, 3D printing technology was used to reduce the wastage and to cover defective regions in leather. The present study focuses on synthesis of acrylic binder using emulsion polymerization technique. These binders were analysed for solid content for better optimisation of the amount of binder to be utilised for finishing operation. The experimental binder was prepared with 26% solids. Particle size and thermogravimetric analyses were carried out to understand the size and shape of the particles and their thermal resistance. These binders were used for leather finishing and the performance of leather was studied. Surface morphology changes of leathers were studied using Scanning Electron Microscopy (SEM). Wet and dry rub fastness, finish film adhesion, light fastness and organoleptic properties were studied and found to be superior compared with control leathers. The acrylic finished leather with minor defects was taken for 3D printing and designed using Thermoplastic Polyurethane (TPU) as filament. The acrylic finished leather shows good adhesion for TPU and it results in numerous designs in short duration. The new additive was added to leather using 3D printing technology to produce a tailor-made valuable design without any waste disposal and chemical discharge. This invention may convert the rejected waste leather into valuable material and lead to the new generation hybrid leather for use.

Acrylates-based hydrophilic co-polymeric nanobeads as nanocarriers for imaging agents

Acrylates-based co-polymeric nanoparticles (PNPs) are widely used in nanomedicine applications due to their tunable hydrophilic surface, physical and chemical versatility. Particularly attracting is their use as nanocarriers for imaging agents. Herein, methyl methacrylate (MMA) and N,N-dimethylacrylamide (DMAA) monomers were used to synthesize hydrophilic p(MMA-co-DMAA) nanoparticles in the 200–600 nm size range via surfactant-free radical emulsion polymerization technique. Different MMA/DMAA molar ratios, temperatures, and reaction times were investigated to evaluate their role in determining the average particle size, polydispersity, and optimizing surface properties of PNPs. Nanoparticles formation, stability (in water and culture medium for cell growth), swelling behavior, structural features and molecular weights were assessed by spectroscopic, non-spectroscopic, and chromatographic techniques. Morphological profiles confirming spherical-shaped NPs were obtained at solid state via microscopies (FESEM, AFM). To use such colloids as potential imaging agents, PNPs were loaded with Y3+(aq) ions by the addition of aqueous solutions of YCl3 at different concentrations, and results compared with p(MMA-co-AA)-DTPA NPs (AA = acrylic acid) functionalized with DTPA chelating agent. Yttrium ions loading percentage was ca. 90% for both p(MMA-co-DMAA) and p(MMA-co-AA)-DTPA, with negligible release (<15%) over a month. Parallelly, optical imaging nanoprobes were obtained by physical encapsulation of fluorescein isothiocyanate isomer I (FITC) dye during the synthesis process, and the spontaneous FITC incorporation was evaluated by spectroscopic studies and fluorescence microscopy. Cytotoxicity studies on pristine and yttrium-loaded nanoparticles were done in vitro on human glioblastoma T98G cell line within 24 h of treatment. Transmission electron microscopy (TEM) studies on cancer cells treated with NPs confirmed an active uptake of PNPs through multiple endocytic pathways to reach the perinuclear region of the cell. Overall, this work elucidated the role of synthetic parameters for a rational design of hydrophilic PNPs as nanocarriers for imaging agents with potential applications in theranostics.

Development of levan-coated PIBCA nanoparticles and their antiproliferative activity against MDA-MB-231 and B16F10 cells

Polysaccharides have been described as a successful alternative in developing nanosystems to reach specific sites. Levan is an exopolysaccharide with several biological activities, including immunostimulant, blood plasma substitute, and drug action prolonging agent. The present work aimed to develop poly-isobutyl cyanoacrylate (PIBCA) nanoparticles coated levan (Np-Lev) and to verify its cytotoxicity in two cancer cell lines. Levan was obtained through the fermentation of ZAG 12 Zymomonas mobilis. The nanoparticles were prepared using the anionic emulsion polymerization technique and characterized in size, zeta potential, morphological analysis, X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis. The cell lines MDA-MB-231 (metastatic breast cancer cells) and B16F10 (melanoma cells) were used to evaluate the antiproliferative activity and cellular uptake of Np-Lev. The technique of obtaining the levan allowed a higher yield than the reference methodology, achieving 71.4% more. The novel nanoparticles (Np-Lev) presented spherical shapes, size of 244 ± 2 nm with homogeneous distribution and zeta potential of −12 ± 1 mV. Characterization techniques, such as infrared spectroscopy and X-ray diffraction, confirmed the presence of levan in the nanoparticles. The thermogravimetric analysis results showed greater thermal resistance when compared to free levan. In addition, Np-Lev were more cytotoxic than levan in both cell lines. This toxicity may be related to the internalization of nanoparticles inside the cells since Np-Lev were captured by the cells, which could increase the activity of levan cytotoxicity. Thus, it was verified a substantial increase in levan yield, also that the levan produced could be used to prepare PIBCA nanoparticles, and finally these Np-Lev showed antiproliferative activity against breast cancer and melanoma cell lines. The results exposed here are of interest to explore levan potential, in addition to nanotechnology, as a promising nanosystem with various biological applications. Further studies are needed to understand the biological behavior of nanoparticles and assess their stability for future therapeutic application.

Temperature and pH-responsive PNIPAM@PAA Nanospheres with a Core-Shell Structure for Controlled Release of Doxorubicin in Breast Cancer Treatment

Stimuli-responsive polymers have been of great interest in the fabrication of advanced drug delivery systems. In this study, a facile approach was developed to synthesize a dually temperature/pH-responsive drug delivery system with a core-shell structure to control the release of doxorubicin (DOX) at the target site. For this purpose, poly(acrylic acid) (PAA) nanospheres were first synthesized using the precipitation polymerization technique and were used as pH-responsive polymeric cores. Then, poly(N-isopropylacrylamide) (PNIPAM) with thermo-responsivity properties was coated on the outer surface of PAA cores via seed emulsion polymerization technique to render monodisperse PNIPAM-coated PAA (PNIPAM@PAA) nanospheres. The optimized PNIPAM@PAA nanospheres with an average particle size of 116.8 nm (PDI= 0.243), had a high negative surface charge (zeta potential= -47.6 mV). Then, DOX was loaded on PNIPAM@PAA nanospheres and the entrapment efficiency (EE) and drug loading (DL) capacity were measured to be 92.7% and 18.5%, respectively. The drug-loaded nanospheres exhibited a low leakage at neutral pH and physiological temperature, but drug release significantly enhanced at acidic pH (pH= 5.5), indicating the tumor-environment responsive drug release behavior of the prepared nanospheres. Also, kinetics studies showed that, the sustained release of DOX from PNIPAM@PAA nanospheres was consistent with the Fickian diffusion mechanism. Moreover, the anticancer efficacy of DOX-loaded nanospheres was evaluated in vitro against MCF-7 breast cancer cells. The obtained results revealed that, the incorporation of DOX into PNIPAM@PAA nanospheres increases its cytotoxicity against cancer cells compared to the free DOX. Our results suggest that, PNIPAM@PAA nanospheres can be considered as a promising vector to release anticancer drugs with dual-stimuli responsivity to pH and temperature.